Insecticidal and acaricidal phenylhydrazone derivatives

ABSTRACT

Phenylhydrazone derivatives of the formula: WHEREIN R represents alkyl of 1 to 10 carbon atoms and Ar represents phenyl substituted by three atoms or radicals selected from halogen, alkyl or 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkenyloxy of 2 to 4 carbon atoms and alkynyloxy of 2 to 4 carbon atoms, at least one of the substituents on the phenyl radical being an alkoxy, alkenyloxy or alkynyloxy radical, which are new compounds, possess insecticidal and acaricidal properties.

United States Patent 1191 Boesch Nov. 4, 1975 INSECTICIDAL AND ACARICIDAL PHENYLHYDRAZONE DERIVATIVES [75] Inventor: Roger Boesch, Vitry-sur-Seine,

[62] Division of Ser. No. 363,652, May 24, 1973, Pat. No.

[30] Foreign Application Priority Data May 26, 1972 France 72.18895 Mar. 19, 1973 France 73.09753 [52] us. Cl. 424/327; 424/304 [51] Int. Cl. A01N 9/20; AOlN 9/24 [58] Field of Search 424/327; 260/566 B [56] References Cited UNITED STATES PATENTS 3,150,151 9 1964 Urbschat et al. 260/3265 3,636,112 1/1972 Draber et a1. 260/566 B 3,786,131 1/1974 Buchel et al....

3,809,675 5/1974 Hansen 260/459 R OTHER PUBLICATIONS Chemistry of Organic Compounds (Textbook) Noller, p. 234, 3rd ed., (1965) Primary Examiner-Albert T. Meyers Assistant Examiner-Leonard Schenkman Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher ABSTRACT Phenylhydrazone derivatives of the formula:

wherein R represents alkyl of 1 to l0 carbon atoms and Ar represents phenyl substituted by three atoms or radicals selected from halogen, alkyl or 1 to 4 carbon atoms, alkox-y 10f l to 4 carbon atoms, alkenyloxy of 2 to 4 carbon atoms and alkynyloxy of 2 to 4 carbon atoms, at least one of the substituents on the phenyl radical being an alkoxy, alkenyloxy or alkynyloxy radical, which are new compounds, possess insecticidal and acaricidal properties.

21 Claims, No Drawings 1 INSECTICIDAL AND ACARICIDAL PHENYLHYDRAZONE DERIVATIVES This is a division of application Ser. No. 363,652, filed May 24, 1973, now US. Pat. No. 3,839,445.

This invention relates to new phenylhydrazone derivatives, to a process for their preparation and to compositions containing them.

The phenylhydrazone derivatives of the present invention are those of the general formula:

wherein R represents an alkyl radical containing 1 to '10 carbon atoms, and Ar represents a phenyl radical substituted by three atoms or radicals, which may be the same or different, selected from halogen (preferably chlorine) atoms, alkyl radicals containing 1 to 4 carbon atoms, alk xy radicals containing 1 to 4 carbon atoms, alkenyloxy radicals containing 2 to 4 carbon atoms and alkynyloxy radicals containing 2 to 4 carbon atoms, at least one of the substituents on the phenyl radical being an alkoxy, alkenyloxy or alkynyloxy radical. It is to be understood that alkyl radicals represented by symbol R, and alkyl, alkoxy, alkenyloxy and alkynyloxy radicals present on the phenyl radical Ar may have straightor branched-carbon chains.

According to a feature of the invention, the phenylhydrazone derivatives of general formula I are prepared by the action of a chlorinating agent, such as phosphorus pentachloride, phosphorus oxychloride or thionyl chloride, on a phenylhydrazide of the general formula:

ArNH-NHCOR -n wherein R and Ar are as hereinbefore defined.

Preferably phosphorus pentachloride is used as the chlorinating agent and the reaction can then be represented schematically in the following manner:

2 When thionyl chloride is employed as the chlorinating agent the reaction can be represented schematically as follows:

R COOH lll (wherein R is as hereinbefore defined), or a derivative of the acid, such as a halide or the anhydride, on a phenylhydrazine of the general formula:

wherein Ar is as hereinbefore defined. The reaction is generally carried-out in an inert organic solvent such as methylene chloride, ethyl acetate or an aromatic hydrocarbon such as. benzene.

The phenylhydrazines of general formula N can be obtained by diazotization of an aniline of the general formula Ar NH v (wherein Ar is as hereinbefore defined) and reduction of the resulting diazonium salt.

The phenylhydrazone derivatives of general formula I obtained by the afore-described process can optionally be purified by application of physical methods such as crystallisation or chromatography.

CI OP Cl Cl wherein the symbols R and Ar are as hereinbefore defined, and Ar, represents a phenyl radical which is optionally substituted, for example by an alkyl radical.

Conversion of the grouping Nl-l-COR in the phenylhydrazides of general formula II into a grouping The new compounds of general formula I possess particularly interesting insecticidal and acaricidal properties. The insecticidal activity is manifest more particularly by contact against diptera (Musca domestica), coleoptera (Tribolium confusum) and lepidoptera (Plutella maculipennis caterpillars) at doses between 10 and g. of active material per hectoliter of liquid diluent. The acaricidal activity is interesting against phytophagous acarids (Tetranych us telarius) at doses between 1 and 100 g. of active material per hectoliter of liquid diluent. At doses between 1 and 200 g. of active material per hectoliter of liquid diluent, the phenylhydrazone derivatives of general fomtula I show a considerable ovidical activity.

Of particular interest are those phenylhydrazone derivatives of general formula I in which the three substituents on the phenyl nucleus are in positions 2-, 4- and 5- and which can be represented by the general formula:

wherein R represents an alkyl radical containing 1 to 4 carbon atoms, R represents a halogen atom or an alkoxy radical containing 1 to 4 carbon atoms, or an al kenyloxy or'alkynyloxy radical containing 2 to 4 car bon atoms, R represents a halogen'atom, or an alkyl or alkoxy radical containing l to 4 carbon atoms, or an alkenyloxy or alkynyloxy radical containing 2 to 4carbon atoms, one of the symbols R and R representing an alkoxy, alkenyloxy or alkynyl o xy radical, and R represents a halogen atom, preferably chlorine. When one of the symbols R and R represents a halogen atom, the atom is preferably chlorine.

Compounds of general formula VI of outstanding importance are those in which R represents the methyl, ethyl, propyl, isopropyl, isobutyl or t.-butyl radical, R represents an isopropoxy, allyloxy or propargyloxy radical, and R and R represent chlorine atoms, forexample l-( 2,4-dichloro-5-propargyloxyphenyl-hydrazono l-chloro-2-methylpropane,

l-( 2,4-die hloro-5-propargyloxyphenyl-hydrazono l-chloro-2 ,Z-dimethylpropane,

l-( 2,4-dichloro-5-propargyloxyphenyl-hydrazono l -chloroethane, l-( 2,4-dichloro-5-isopropoxyphenyl-hydrazono)- l chloro-2-methylpropane, y l-( 2,4dic hloro-5-propargyloxyphenyl-hydrazono v l-chloropropane,

l-( 2,4-dichloro-5-propargyloxyphenybhydrazono l-chloro -.3 -methylbutane,

l-( 2,4-dichloro-5-isopropoxyphenyl-hydrazono)a l chlorobutane,

l-( 2,4-dichloro-5-isopropoxyphenyl-hydrazono lchloro-3-methylbutane,

l-( 2,4-die hloro-5-propargyloxyphenyl-hydrazono l -chlorobutane,

l-( 2,4-dichloro-5-isopropoxyphenyl-hydrazono)- l chloro-2,Z-dimethylpropane,

l-( 2,4-dichloro-5-allyloxyphenyl-hydrazono)- l chloro-2,2-climethylpropane,

1-( 2,4-dichloro-S-allyloxyphenyl-hydrazono 1 chloroethane and l-( 2,4-dichloro-5-isopropoxyphenyl-hydrazono l chloropropane, i especially the first-mentioned compound.

According to a further feature of the present invention, there are provided insecticidal and acaricidal compositions which contain, as the active ingredient, at least one of the phenylhydrazone derivatives of general formula I in association with one or more diluents or adjuvants compatiblewith' the phenylhydrazone derivative(s) and suitable for use in agriculture.

These compositions can optionally contain other compatible pesticides such as fungicides (e.g. maneb). Preferably the compositions contain between 0.005% and 80% by weight of phenylhydrazone derivative.

The compositions may be solid if there isemployed a powdered solid compatible diluent such as talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent charcoal, or a clay such as kaolin or bentonite. These solid compositions are preferably prepared by grinding the phenylhydrazone derivative with the solid diluent, or by impregnating the solid diluent with a solution of the phenylhydrazone derivative in a volatile solvent, evaporating the solvent, and if necessary grinding the product so as to obtain a powder.

Instead of a solid diluent, there may be used a liquid in which the phenylhydrazone derivative is dissolved or dispersed. The compositions may thus take the form of suspensions, emulsions orsolutions in organic or aqueous-organic media, for example aromatic hydrocarbons such as toluene or xylene, mineral, animal or vegetable oils, or acetophenone, or mixtures of these diluents. The compositions in the form of suspensions, emulsions or solutions may contain wetting, dispersing or emulsifying agents of the ionic or non-ionic type, for example sulphoricinoleates, quaternary ammonium derivatives or products based on condensates of ethylene oxide such as the condensates of ethylene oxide with octylphenol, or fatty acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxyl groups by condensation with ethylene oxides. It is preferable to use agents of the non-ionic type because they are not sensitive to electrolytes. When emulsions are required the phenylhydrazone derivatives may be-used in the form of self-emulsifying concentrates containing the active substance dissolved in the emulsifying agentor in a solvent containing an emulsifying agent compatible with the phenylhydrazone derivative and solvent, a simple addition of water to such concentrates producing compositions ready for use.

The phenylhydrazone derivatives of general formula I are preferably employed for insecticidal and acaricidal purposes in quantities of 10 to g. per hectoliter of water, but lower concentrations can also be used effectively.

The following Example illustrates the preparation of phenylhydrazone derivatives of general formula I.

EXAMPLE 1 A suspension of l-isobutyryl-2-(2,4-dichloro-5- propargyloxyphenyl)hydrazine (30.1 g.) and phosphorus pentachloride (21.5 g.) in carbon tetrachloride (200 cc.) is heated under reflux until the evolution of gas ceases. To the solution obtained there is added, after cooling to 20C., phenol (32.4 g.) dissolved in carbon tetrachloride (1 15 cc.) and the mixture is then heated until the evolution of gas ceases whilst taking the reaction mixture progressively to the reflux temperature. The solvent is evaporated under reduced pressure (20 min Hg) at 50C and the residual solid is stirred with di-isopropyl ether (100 cc.). The crystals which are formed are filtered off, washed with di-isopropyl ether cooled to 5C. (2 X 10cc.) and dried under reduced pressure (0.5 mm Hg) at 20C to yield 1-( 2,4 -dichloro-5-propargyloxyphenyl-hydrazono) l chloro-2-methylpropane (23 g.) melting at 103C.

1 -lsobutyryl-2-( 2,4-dichloro-5-propargyloxyphenyl hydrazine (mp. 162 and then 169C), which is employed as starting material, can be obtained by the action of isobutyryl 'chloride on 2,4-.dichloro-j5-propargyloxyphenyl-hydrazine in ethyl acetate in the presence of triethylamine. a v I 2,4-Dichloro 5-propargyloxyphenyl-hydrazine, mp.

132C, can be obtained by the action of sodium nitrite on 2,4-dichloro-5-propargyloxy-aniline in hydrochloric acid ((1 1.18) followed by reduction of the diazonium salt thus formed with stannous chloride.

5 2,4-Dichloro-5-propargyloxy-aniline, m.p. 90C., can be prepared by the reduction of the corresponding nitro derivative by means of iron in aqueous ethanol.

2,4-Dichloro-5-propargyloxy-nitrobenzene, 66C., can be prepared by the action of propargylchlo ride on 2,4-dichloro-5-nitrophenol in acetonitr'ile under reflux in the presence of potassium carbonate;

By proceeding'as described in the foregoing Example and starting with appropriate phenylhydrazides of general formula 11, there can be prepared the following phenylhydrazone derivatives conforming to' general formula 1: r 5

l-( 2,4-dichloro 5-propargyloxyphenyl-hydrazono l-(-2,4-dic hloro-5-isopropoxyphenyl-hydrazono) l A g chlorobutane, an oil; r l-( 2,4-dichlro-5-isopropoxyphenyl:hydrazono 1 chloroheptane, an oil;

l-( 2,4-dichloro--isopropoxyphenyl-hydrazono l I chlorooctane, an oil; v

l-(2,4-dichloro-5-isopropoxyphenyl-hydrazono 1- chloro-3-methylbutane, an oil; I

l-(2,4-dichloro-5-propargyl0xyphenyl-hydrazono)- l-chlorobutane, an oil; v

1-( 2,4-dic hloro-5-isopropoxyphenyl-hydrazono 1- chloro-2,2-dimethylpropane, solidification point 34C.; m I

1-( 2,4-dichloro-S-methoxyphenyl-hydrazono)- 1 I chloropropane, m.p. 70,7.lC.;

l-( 2,4-dic hloro-5-methoxyphenyl-hydrazono l ch1oro-2,Z-dimethylpropane, m.p. l l8-119C.;

1-( 2,4-dichloro-S-allyloxyphenyl-hydrazono)- l chloro-2,2-dimethylpropane, m.p. 87C.;

l-(2,4-dichloro-5-methoxyphenyl-hydrazono)-1- chlorobutane, m.p. 70C.;

1-( 2,4-dic hloro-5-allyloxyphenyl-hydrazono l chloroethane, m.p. 87C.;

l-(2,4-dichloro-S-isopropoxyphenyl-hydrazono)-1- chloropropane, solidification point 27C.;

I-( 2,4-dichloro-5-sec-butoxyphenyl-hydrazono)- l chloroethane, m.p. 47C.;

l-( 2,4-dichloro-5-sec-butoxyphenyl-hydrazono 1- chloropropane, solidification point 27C.;

l-( 2,4-dichloro-5-sec-butoxyphenyl-hydrazono 1- chlorobutane, solidification point 29C.;

1-( 2,4-dic hloro-5-sec-butoxyphenyl-hydrazono 1- chloro-2-methypropane, an oil;

1-( 2,4-dic hloro-S-ethoxyphenyl-hydrazono lchloropropane, m.p. 64, then 67C.;

l-(2,4-dichloro-5-ethoxyphenyl-hydrazono)-1- chlorobutane, m.p. 77C.;

1-( 2,4-dic hloro-S-eth0xyphenyl-hydrazono)- l chloro-2-methylpropane, m.p. 68C.;

l-(2,4-dichloro-5-ethoxyphenyl-hydrazono)-1- chloro-2,2-dimethylpropane, m.p. l21 C.;

l-( 2,5-dic hloro-4-propargyloxyphenyl-hydrazono l-chloro-2,Z-dimethylpropane, m.p. 71C.;

6 l-( 2-chloro-4-methyl-5-propargyloxyphenylhydrazono)-l chlorobutane, m.p. 57C.; 1 2,5-dichloro-4-propargyloxyphenyl-hydrazono l-ch1oro-2-methylpropane, m.p. 94C.; l-( 2-chloro-4-methyl -5-propargyloxyphenylhydrazono)-l-chloropropane, m.p. 74C.; 1-( 2-chloro-4-methyl-5 -propargyloxyphenylhydrazono)-l-chloroethane, m.p. C.; l-( 2,5-dichloro-4-pro pargyloxyphenyl-hydrazono l-chloroetha'ne, m.p. 103C; l 2,5-dichloro 4-propargyloxyphenyl-hydrazono l-chloropropane, m.p. 87C., and 1-(2,5-dichloro-4'-propargyloxyphen yl-hydrazono l-chlorobutane, solidification point 38C. The pi'oducts obtained as oils are characterised by elementary analysis and infra red spectra.

EXAMPLE 2- EXAMPLE 3 To 50 parts of l-(2,4-dichloro-5wpropargyloxyphenyl-hydrazono 1 -chloro-2-methylpropane there are added 1 part of Tween 80v (the mono-oleate of a polyoxyethylene derivative of sorbitol), 20 parts of calcium lignosulphite and 29 parts of kieselguhr. After grinding and sieving,.the powder obtained is utilised afterdilution with water to destroy acarids.

The parts referred to above are parts by weight.

I claim:

1. An insecticidal and acaricidal composition which contains, as the active ingredient, a phenylhydrazone derivative of the formula:

wherein R represents alkyl of 1 through 10 carbon atoms and Ar represents phenyl substituted by three substituents which may be the same or different and are selected from the group consisting of halogen, alkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, alkenyloxy of 2 through 4 carbon atoms and alkynyloxy of 2 through 4 carbon atoms, at least one of the substituents on the phenyl radical being an alkoxy, alkenyloxy or alkynyloxy radical, in association with one or more diluents or adjuvants compatible with the phenylhydrazone derivative and suitable for use in agricultural insecticidal and acaricidal compositions, the quantity of phenylhydrazone derivative in the composition being 0.005 to 80% by weight of the composition.

2. A composition according to claim 1 in which the diluent is water and the composition containslO to g. of phenylhydrazone derivative per hectoliter of water.

phenylhydrazone derivative is l-(2,4-dichloro-- propargyloxyphenyl-hydrazono l -chloro-2-methylpropane.

7. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5- propargyloxyphenyl-hydrazono 1 -chloro-2,2-dimethylpropane.

8. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5- propargyloxyphenyl-hydrazono l -chloroethane.

9. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5-isopropoxyphenyl-hydrazono l -chloro-2-methylpropane.

10. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5- propargylox yphenyl-hydrazono l chloropropane.

11. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5- propargyloxyphenyl-hydrazono l -chloro-3-methylbutane.

12. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5-isopropoxyphenyl-hydrazono l -chlorobutane.

13. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5-isopropoxyphenyl-hydrazono l -chloro-3-methylbutane.

14. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5- propargyloxyphenyl-hydrazono)- l -chlorobutane.

15. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5-iso- 8 propoxyp henyl-hydrazo no 1-chloro-2,2-dimethylpropane.

16. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5- allyloxyphenyl-hydrazo no 1-chloro-2 ,Z-dimethylpropane.

17. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5- allyloxyphenyl-hydrazono)- l -chloroethane.

18. A composition according to claim 1 wherein the phenylhydrazone derivative is l-(2,4-dichloro-5-isopropoxyphenyl-hydrazo no l-chloropropane.

19. A composition according to claim 1 wherein the phenylhydrazone derivative has the formula:

wherein R represents alkyl of 1 through 4 carbon atoms, R represents halogen, alkoxy of 1 through 4 carbon atoms, or alkenyloxy or alkynyloxy of 2 through 4 carbon atoms, R represents halogen, alkyl or alkoxy of 1 through 4 carbon atoms, or alkenyloxy or alkynyloxy of 2 through 4 carbon atoms, one of the symbols R and R represents alkoxy, alkenyloxy or alkynyloxy, and R represents halogen.

20. A composition according to claim 19 wherein one of the symbols R and R represents chlorine and the other represents alkoxy, alkenyloxy or alkynyloxy, and R represents chlorine.

21. A composition according to claim 19 in which R represents methyl, ethyl, propyl, isopropyl, isobutyl or t.-butyl, R represents isopropoxy, allyloxy or propargyloxy, and R and R represent chlorine. 

1. AN INSECTICIDAL AND ACARICIDAL COMPOSITION WHICH CONTAINS, AS THE ACTIVE INGREDIENT, A PHENYLHYDRAZONE DERIVATIVE OF THE FORMULA:
 2. A composition according to claim 1 in which the diluent is water and the composition contains 10 to 100 g. of phenylhydrazone derivative per hectoliter of water.
 3. A composition according to claim 1 which contains a wetting agent.
 4. A composition according to claim 3 in which the wetting agent is a non-ionic compound.
 5. A composition according to claim 1 wherein one or more halogen substituent on the phenyl radical is chlorine.
 6. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1-chloro-2-methylpropane.
 7. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1-chloro-2,2 -dimethylpropane.
 8. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1-chloroethane.
 9. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-isopropoxyphenyl-hydrazono)-1-chloro-2-methylpropane.
 10. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1-chloropropane.
 11. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1-chloro-3-methylbutane.
 12. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-isopropoxyphenyl-hydrazono)-1-chlorobutane.
 13. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-isopropoxyphenyl-hydrazono)-1-chloro-3-methylbutane.
 14. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1-chlorobutane.
 15. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-isopropoxyphenyl-hydrazono)-1-chloro-2,2-dimethylpropane.
 16. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-allyloxyphenyl-hydrazono)-1-chloro-2,2-dimethylpropane.
 17. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-allyloxyphenyl-hydrazono)-1-chloroethane.
 18. A composition according to claim 1 wherein the phenylhydrazone derivative is 1-(2,4-dichloro-5-isopropoxyphenyl-hydrazono)-1-chloropropane.
 19. A composition according to claim 1 wherein the phenylhydrazone derivative has the formula:
 20. A composition according to claim 19 wherein one of the symbols R1 and R2 represents chlorine and the other represents alkoxy, alkenyloxy or alkynyloxy, and R3 represents chlorine.
 21. A composition according to claim 19 in which R'' represents methyl, ethyl, propyl, isopropyl, isobutyl or t.-butyl, R1 represents isopropoxy, allyloxy or propargyloxy, and R2 and R3 represent chlorine. 